The present invention relates to liquid personal wash compositions to effectively deposit solid particles comprising (a) surfactant (synthetic surfactant with or without soap); (b) large particle-in-oil dispersions comprising (i) a solid particle (0.1 to 150 microns, preferably 0.2 to 100 microns) or (ii) a capsule in either petrolatum or in a hydrocarbon oil which is thickened or structured with an oil-mixable polymer; and (c) water soluble thickener mixable with the surfactant (e.g., concentrated surfactant) which can prevent physical separation of the large particle-in-oil dispersions (dispersions having size greater than 50 microns) and are capable of preventing separation of large particle-in-oil dispersions for over 3 months.
Deposition of emollient oils from liquid cleansers can be achieved using small droplet deposition assisted with cationic polymer or by using large drops. However, deposition of solid particles (e.g., hydrophilic particle) from a cleansing product (e.g., wash-off cleanser) remains technically challenging.
U.S. Pat. No. 5,661,189 to Grieveson discloses an aqueous liquid and a moisturizing composition containing emollients thickened with a hydrophobic thickener which emollients have a particle in the range of 50-500 xcexc. These are thickened particles, not particle in oil dispersions.
U.S. Pat. No. 5,804,540 to Tsaur discloses personal wash liquids comprising low viscosity oils pre-thickened by non-antifoaming hydrophobic polymers.
Again, the reference fails to teach or suggest solid cosmetic particles or capsules as particle-in-oil dispersions. Further, there is no disclosure of a particle-in-oil dispersion in a surfactant system comprising water soluble thickener mixable with surfactant.
U.S. Pat. No. 5,869,070 to Dixon et al. discloses stable liquid cleansing compositions with skin moisturizing agent and gel forming polymer. Skin moisturizing agents are petrolatum, polybutene and mixtures of petrolatum/polybutene with ratio of 3:1 to 5:1.
The reference fails to disclose solid, particle (e.g., cosmetic particle) in oil or capsules in oil. Further, although petrolatum/polybutylene is disclosed as moisturizer, there is no teaching or suggestion of a separate oil thickened by petrolatum/polybutylene. Finally, there is no teaching or suggestion of particle-in-oil found in a thickened/concentrated surfactant system.
U.S. Pat. No. 5,912,002 to Grieveson et al. discloses cleansing composition comprising surfactant and internal emulsion comprising cosmetic agent, emulsifier and carrier.
Grieveson differs from the compositions of the invention in that compositions of the subject invention require that the oil (of xe2x80x9cparticle in oilxe2x80x9d) is capable of separating and entrapping solid particles in presence of concentrated surfactant solution and without need of emulsifier. By contrast, Grieveson is an oil-in-oil emulsion where stability is achieved only by using an emulsion. Further, the oil (carrier oil) of Grieveson can be any oil in the range of 200 to 500,000 centistokes at 25xc2x0 C while, in the subject invention, oil viscosity must be higher than 10,000 centistokes at 0.1 Sxe2x88x921.
Unexpectedly, applicants have now found a superior way to deliver (a) solid particles; and/or (b) capsule (e.g., perfume-containing capsules) from a wash-off liquid by forming a particle-in-oil dispersion; wherein particle refers to any of (a) or (b) above; wherein the oil is petrolatum; or emollient oils which contain an oil mixable polymer; and wherein the surfactant system in which the particle-in-oil dispersion is found is thickened/concentrated (e.g., with xanthan gum or other thickener). The particle-in-oil dispersion remains stable at room temperature for greater than 3 months with no visible physical separation and, in use, deposits far greater amounts of solid particle/capsule from a wash-off liquid composition than would be possible if the particles were added alone rather than as particle-in-oil dispersion.
More specifically, the invention comprises:
A personal liquid composition comprising:
(1) 5% to 30%, preferably 8% to 25% by wt. of a surfactant selected from the group consisting of anionic surfactants, amphoteric surfactants, nonionic surfactants, cationic surfactants and mixtures thereof;
(2) 0.5% to 5% by wt. of a water soluble thickener mixable with said surfactant(s) and which prevents physical separation of a particle-in-oil dispersion as noted in (3) below from the liquid cleanser for three months or more as measured at room temperature; and
(3) 2% to 20% by wt. of said particle-in-oil dispersion comprising:
(a) 60% to 99% by wt. of said dispersion of petrolatum; or hydrocarbon oil containing oil mixable polymer, wherein said petrolatum or polymer containing oil can suspend solid particles having density greater than 1.05 (without need of an emulsifier, although such emulsifier may be optionally added if desired);
(b) 1% to 40% by wt. of a xe2x80x9cparticlexe2x80x9d selected from the group consisting of (i) solid particles with particle size in range 0.1 to 250, preferably 0.2 to 100 microns; and (ii) capsules with size in the range of 1-200 microns,
wherein the particle-in-oil dispersion is itself stable at room temperature for over 3 months;
wherein the particle-in oil dispersion has size of about 50 to 5000 microns, preferably 100-1000 microns; and
wherein particle-in-oil dispersion is stable in the composition for three months or more at R.T.
The present invention relates to compositions for delivering solid particles (preferably hydrophilic solid particles) and/or capsules (e.g., perfume-containing capsules) from wash off liquid compositions. These xe2x80x9cparticlesxe2x80x9d (referring generally to the solid particles, and capsules) are delivered from relatively large size (50 to 5000 microns), stable (for at least three months at room temperature), particle-in-oil dispersions found in thickened/concentrated surfactant compositions wherein the entire composition (containing particle-in-oil dispersion) is itself stable for three months at room temperature.
The compositions, as described below, will be defined by (a) surfactant system; (2) thickening system for said surfactant system; and (3) particle-in-oil composition wherein the particle-in-oil composition is itself defined by (a) particles (e.g., solid particle or capsules) and (b) oil in which particles are found. The oil is petrolatum; or oil containing oil-mixable polymers to help further suspend/stabilize particles.
The invention is thus defined in more detail below.
The composition of the invention comprises 5 to 30% by wt. surfactant. The surfactants in the composition may be anionic, nonionic, amphoteric/zwitterionic, cationic or mixtures thereof.
The anionic surfactant may be, for example, an aliphatic sulfonate, such as a primary alkane (e.g., C8-C22) sulfonate, primary alkane (e.g., C8-C22) disulfonate, C8-C22 alkene sulfonate, C8-C22 hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate (AGES); or an aromatic sulfonate such as alkyl benzene sulfonate.
The anionic may also be an alkyl sulfate (e.g., C12-C18 alkyl sulfate) or alkyl ether sulfate (including alkyl glyceryl ether sulfates). Among the alkyl ether sulfates are those having the formula:
RO(CH2CH2O)nSO3M
wherein R is an alkyl or alkenyl having 8 to 18 carbons, preferably 12 to 18 carbons, n has an average value of greater than 1.0, preferably between 2 and 3; and M is a solubilizing cation such as sodium, potassium, ammonium or substituted ammonium. Ammonium and sodium laurel ether sulfates are preferred.
These differ from ether sulfates of the invention in that they are not branched.
The anionic may also be alkyl sulfosuccinates (including mono- and dialkyl, e.g., C6-C22 sulfosuccinates); alkyl and acyl taurates, alkyl and acyl sarcosinates, sulfoacetates, C8-C22 alkyl phosphates and phosphates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates, C8-C22 monoalkyl succinates and maleates, sulphoacetates, and acyl isethionates.
Sulfosuccinates may be monoalkyl sulfosuccinates having the formula:
R4O2CCH2CH(SO3M)CO2M;
amido-MEA sulfosuccinates of the formula
R4CONHCH2CH2O2CCH2CH(SO3M)CO2M
wherein R4 ranges from C8-C22 alkyl and M is a solubilizing cation; amido-MIPA sulfosuccinates of formula
RCONH(CH2)CH(CH3)(SO3M)CO2M
where M is as defined above.
Also included are the alkoxylated citrate sulfosuccinates; and alkoxylated sulfosuccinates such as the following: 
wherein n=1 to 20; and M is as defined above.
Sarcosinates are generally indicated by the formula RCON(CH3)CH2CO2M, wherein R ranges from C8 to C20 alkyl and M is a solubilizing cation.
Taurates are generally identified by formula
xe2x80x83R2CONR3CH2CH2SO3M
wherein R2 ranges from C8-C20 alkyl, R3 ranges from C1-C4 alkyl and M is a solubilizing cation.
Another class of anionics are carboxylates such as follows:
R-(CH2CH2O)nCO2M
wherein R is C8 to C20 alkyl; n is 0 to 20; and M is as defined above.
Another carboxylate which can be used is amido alkyl polypeptide carboxylates such as, for example, Monteine LCQ(copyright) by Seppic.
Another surfactant which may be used are the C8-C18 acyl isethionates. These esters are prepared by reaction between alkali metal isethionate with mixed aliphatic fatty acids having from 6 to 18 carbon atoms and an iodine value of less than 20. At least 75% of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25% have from 6 to 10 carbon atoms.
Acyl isethionates, when present, will generally range from about 0.5-15% by weight of the total composition. Preferably, this component is present from about 1 to about 10%.
The acyl isethionate may be an alkoxylated isethionate such as is described in llardi et al., U.S. Pat. No. 5,393,466, hereby incorporated by reference into the subject application. This compound has the general formula:
In general the anionic component will comprise from about 1 to 20% by weight of the composition, preferably 2 to 15%, most preferably 5 to 12% by weight of the composition. It may also include a C8 to C14 unbranched fatty acid hydrocarbon (e.g., lauric acid, palmitic acid, capric, etc.).
Zwitterionic surfactants are exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is: 
wherein R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety; Y is selected from the group consisting of for example nitrogen, atoms; R3 is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus atom; R4 is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
Amphoteric detergents which may be used in this invention include at least one acid group. This may be a carboxylic or a sulphonic acid group. They include quaternary nitrogen and therefore are quaternary amido acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms. They will usually comply with an overall structural formula: 
where R1 is alkyl or alkenyl of 7 to 18 carbon atoms;
R2 and R3 are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms;
n is 2 to 4;
m is 0 to 1;
X is alkylene of 1 to 3 carbon atoms optionally substituted with hydroxyl, and
Y is xe2x80x94CO2xe2x80x94 or xe2x80x94SO3xe2x80x94
Suitable amphoteric detergents within the above general formula include simple betaines of formula: 
and amido betaines of formula: 
where m is 2 or 3.
In both formulae R1, R2 and R3 are as defined previously. R1 may in particular be a mixture of C12 and C14 alkyl groups derived from coconut so that at least half, preferably at least three quarters of the groups R1 have 10 to 14 carbon atoms. R2 and R3 are preferably methyl.
A further possibility is that the amphoteric detergent is a sulphobetaine of formula 
or 
where m is 2 or 3, or variants of these in which xe2x80x94(CH2)3SOxe2x80x943 is replaced by 
In these formulae R1, R2 and R3 are as discussed previously.
Amphoacetates and diamphoacetates are also intended to be covered in possible zwitterionic and/or amphoteric compounds which may be used.
The surfactant system may also optionally comprise a nonionic surfactant.
The nonionic which may be used includes in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6-C22) phenols-ethylene oxide condensates, the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
The nonionic may also be a sugar amide, such as a polysaccharide amide. Specifically, the surfactant may be one of the lactobionamides described in U.S. Pat. No. 5,389,279 to Au et al. which is hereby incorporated by reference or it may be one of the sugar amides described in U.S. Pat. No. 5,009,814 to Kelkenberg, hereby incorporated into the subject application by reference.
Other surfactants which may be used are described in U.S. Pat. No. 3,723,325 to Parran Jr. and alkyl polysaccharide nonionic surfactants as disclosed in U.S. Pat. No. 4,565,647 to Llenado, both of which are also incorporated into the subject application by reference.
Preferred alkyl polysaccharides are alkylpolyglycosides of the formula
xe2x80x83R2O(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 0 to 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from 1.3 to about 10, preferably from 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
Nonionic generally comprises 0 to 10% by wt. of the composition.
Cationic synthetic surfactant should not serve as the sole surfactant in this product, but cam be used as a co-surfactant at a lower level of from about 0.5% to about 6% by weight. The more preferred types of cationic surfactant are selected from the group consisting of: alkyl trimonnium chloride and methosulfate, and dialkyldimonnium chloride and methyl sulphate, and alkyl alkonium chloride and methyl sulphate and mixtures thereof. These surfactants contain C12 to C24 carbon atoms per alkyl chain. The most preferred cationic is selected from the group consisting of stearalkonium chloride, stearyltrimonium chloride. Di-stearyl-dimonium chloride, and mixtures thereof.
Another required component of the invention is organic, inorganic or polymeric stabilizer. Specifically, the compositions comprise 0.1 to 10% by wt. of an organic, inorganic or polymeric stabilizer which provides physical stability of the large oil droplets, (droplets of polymer/oil blend) in the surfactant composition at 40xc2x0 C. for over four weeks.
Generally the organic polymeric stabilizer of the invention include, but are not limited to any of several long chain acyl derivatives or mixtures thereof. Included are the glycol mono- di- and triesters having about 14 to about 22 carbon atoms. Preferred glycol esters include the ethylene glycol mono- and distearates, glyceryl stearates, palm oil glyceride, tripalmitin, tristearin and mixtures thereof. Another example of suspending agent useful in the present invention include the alkanolamides having from about 14 to about 22 carton atoms. Preferred alkanolamides are stearic monoethanolamide, stearic diethanolamide stearic monoisopropanolamide, stearic monoethanolamide stearate and mixtures thereof. Still another example of a suspending agent useful in the present invention include the long chain fatty acid esters such as stearyl stearate, stearyl palmitate, palmityl palmitate, trihydroxystearylglycerol and tristearylglycerol. Still another example of a suitable suspending agent useful in the present invention include the long chain amine oxides having from about 14 to about 22 carbon atoms. Preferred amine oxides are hexadecyldimethylamine oxide and octadecyldimethylamide oxide.
Example of a suitable polymeric suspending agent (or thickening agent) useful in the present invention include the carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, hydroxymethyl carboxymethyl cellulose, hydroxymethyl carboxypropyl cellulose, methyl cellulose, ethyl cellulose, guar gum, gum karaya, gum tragacanth, gum arabic, gum acacia, gum agar, xanthan gum and mixtures thereof. Preferred carbohydrate gums are the cellulose gums and xanthan gum. Of all the above described types of suspending agents, preferred compounds include the long chain glycol ester and the carbohydrate gums. Other stabilizers which may be used are set forth in U.S. Pat. No. 5,854,293 to Glenn, Jr. at column 4, line 36 to column 6, line 65. This reference is hereby incorporated by reference into the subject application.
The thickener may also be a cationic polymer. Suitable cationic polymers include Guar hydroxypropyltrimonium chloride, Quaternium-19, -23, -40, -57, poly(dimethyidiallylammonium chloride), poly (dimethyl butenyl ammonium chloride)-, w-bis (triethanolammonium chloride), poly (dipropyidiallylammonium chloride), poly (methyl-beta propaniodiallylammonium chloride), poly (diallylpiperidinium chloride), poly (vinyl pyridinium chloride), quaternised poly (vinyl alcohol), quaternized poly (dimethylaminoethylmethacrylate) and mixtures thereof.
The suspending agent or mixtures of agent may be present from about 0.1 to 10% of the composition.
While not wishing to be bound by theory, thickener is delivered to aid in suspension of the particle-in-oil dispersion.
Specifically, the thickened surfactant system prevents physical separation of particle-in-oil dispersion for over three months.
The particle-in-oil dispersion comprises solid particles and well-structured oil that can stably suspend and entrap the solid particles in a concentrated surfactant solution. Stability of the particle-in-oil dispersion is achieved by the viscosity and the suspension power of the oil.
The suspended solid particles can be either inorganic or organic particles. Examples of inorganic include but are not limited to silica, talc, mica; and examples organic particles are silicone powders or capsules such as perfume capsules or vitamin E capsules. Capsules suitable for this invention are free flow powders prepared by various encapsulation processes such as interfacial polymerization encapsulation, coacervation encapsulation, spray drying/cooling encapsulation or spray coating encapsulation. These solid particles should be cosmetic grade approved for personal cleansing application. Typically the solid particles will have particle size of 0.1 to 150 microns, preferably 0.2 to 100 microns.
The well-structured oil is defined as emollient oil that has a viscosity higher than 10,000 cps at 0.1 Sxe2x88x921 and can stably suspend the solid particles at room temperature for over 3 months without visible physical separation. Preferably well-structured oil is petrolatum or emollient oil structured/thickened with oil mixable polymers. Examples of emollient oils are mineral oils, triglycerides oils such as sunflower seed oil, castor oil or soybean oil, alkyl esters such as isopropylpalmitate or isopropylmyristate and silicone oils. These emollient oils alone are not useful for the invention due to its poor suspension/entrapping properties. To suspend and entrap dense solid particles, oil mixable polymer is required to add into these emollient oils. The oil mixable polymer works as a thickener and also works as structuring agent to suspend the solid particles. Examples of possible oil mixable polymers are hydrogenated or non-hydrogenated polymer of alkylene or isoalkylene such as polybutene, poly-alphaolefin, or polyester, polyacrylate and it""s copolymer, and rubber thermoplastic block copolymers such as butadiene/styrene or styrene/butylene di- or tri-block copolymers. Most preferably oil mixable polymers are rubber based thermoplastic block polymers available from Shell Chemical Company under the tradename of Kraton(copyright).
In general, the oil drop should be 5 times or greater (i.e., at least 5 times as great) as the size of the suspended particles.
Typically the well structured oil comprises 60% to 99%, preferably 70% to 95% of the particle-in-oil dispersion and the solid particle comprises 1% to 40%, preferably 5% to 30% of the dispersion.
In addition to ingredients noted above, the composition (i.e., surfactant composition) may comprise any one of various ingredients which may be found in personal wash compositions, including organic solvents (e.g., polyols such as C1 to C4 alkanols), auxiliary thickeners, sequestering agents (e.g., tetrasodium ethylenediaminetetraacetate), coloring agents, opacifiers, and pearlizers.
The compositions may also include antimicrobial agents, alkanolamides, antioxidants (e.g., butylated hydroxytoluene), exfoliants (polyoxyethylene beads) etc.
Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts or ratios of materials or conditions or reaction, physical properties of materials and/or use are to be understood as modified by the word xe2x80x9caboutxe2x80x9d.
Where used in the specification, the term xe2x80x9ccomprisingxe2x80x9d is intended to include the presence of stated features, integers, steps, components, but not to preclude the presence or addition of one or more features, integers, steps, components or groups thereof.